Linoleum cements



United S m atent I;

2 8285215 LINOLEUM'GEMENTS Lawrence Hi Dunlap; Lancaster Township, Lancaster (County, Pa'.,. assignor; to Armstrong: Cork Company, Lancaster, Pa.,. a. corporation-.- of-, Pennsylvania No: Drawing. Application November 30, 1951 Serial.No..25.9,311

3-Glaims.- (Cl.- 106-219)- This application isa contiiiliatiori-iir-pait or my" copending, application Serial. No. 81,632,. filed March 15, 1949., .andhow abandoned.

This inventionrelatesto. linoleum compositions... More particularly. .thetinvention'. relates to a linoleum cemeiit comprising, a. resinous. material and a, fraction, ofj an. oil which. 1S5 Substantially completely free from saturated fatty acids.

Linol eumcements have been'rnad for a number. or years from a dr'yin-g oil anus resin By a number or methods which result'in the production of a sicative oil'- resin; gel by? oxidizing: and:- polymerizing: the drying. oil generally; int the-presence: of: the: resinous; material; Ordinar'ily; linoleum. cements: comprise"; about 65% to 85%.

drynngoilaandaahoutzli%:tit-35%resin. For'many'years linoleum cements were manufactured from: a? resin'r such as1ro'sin; arid a; siccativen oil such as a drying oil;. for example linseed; 011;. and a.= semiwdi ying oil; for. example soya: bean. oil. However;. recently; other; materials? have been proposechfor: use: in'rpl'ace: of as pofitionton allaofi the dryingoila component of the: linoleumi cement.v ex:- ample; tall: oilrha-sxbeen so: proposed.

Talk oil.- is; a; by-product: orthe: manufacture: of? k-raft paperby-the: sulfate process; from pine or. fir wood and is generally considered. to be a mixturev of fatty acids, rosin. acids; and. unsaponifiable materials. Generally speaking, a typical% crude: tallv oil: contains: about: 35%; to 50% rosin acids,. about" 40%; tcr 50%; fatty acids; and ab out'.5.% to 1 0%. sterols: Of the fattyacid fraction, saturatedrfattly acids may comprise about:6% to 8570i of. the total; oleic acid'about 44%. to 52%,.and:linoleic:acid about 45 %a to 50% Linoleum cements; containing substantial; quantities'of tall oilhave. been prepared and successfully. employech in the manufacture of linoleum compositions. These compositions may be employed in the preparation-of floor or wall coverings which have generally the flexibility and resilience found in linoleum which is prepared from a siccative oil-resin gel produced by the oxidation and polymerizatioi'r of a drying oil such as linseed oil and a resin such as rosin;

Generally speaking, however, tall oil-containing cements are somewhat more thermoplastic than ordinary linoleum cements; and floorcoverings manufactured from compositions. containing such cements may soften at elevated temperatures, thereby resulting in excessive indentationandafiairly high degree of dirt retention. Thus, these floor coverings. may be adversely affected. in warm climatesor under. extreme. summerv conditions.

I-thas: beenfound that talloil may be treated in such a: manner; as toobtain therefrom a fractionv which, is substantially completely free from saturated. fatty acids.

I have found that. linoleum cements may be. prepared containing the' fraction of tall oil which is. substantially 2,828,215 Patented Mar. 25, 1958 2; completely'free from saturated fatty a'cidsiand-that'z these cements exhibit:- improvedresistance to: indentation under conditions: of elevatedtemperaturessuch as 1 are-normally encounteredin the warmest: of! climates;

The production-of the saturated fatty acidi-freeafraction of tall oil is described in-- application: Serial: No. 81,608, filed M'arch 153 l949, byL. Dunlap and Sievert, now U: S. Patent 2,565,484 and copending: with, my above-identified: copending. application. In accordance with: the invention described-r and claimed in said co? pending application, tall: oil'is first subjectedto' oxidizing conditions until the. viscosity of the material? is: between about 1'51 seconds-arid: 2'5'0 seconds-as: measured in Gard ner H-oldt bubbletubes; The normal: increase; in refractive index oh the tall oil.- when" subjectedv to. such oxidation procedure; is: about .0640: When so= oxidized; the tall oil: is: their subjected: to: solvent extraction" by means of nonpolan solvents or by means of both: non p'olan solvents and: polar! solvents to obtaina fraction containing oxidized unsaturatedifatty acids andwhich isrsub'stantially completely free from saturated; fatty." acids;

More: particularly; as). describedv in said copending application; the-oxidation of the: ta'l-l': oil' may. be carried out in any suitable oxidizing=,equip1nent; and the condis tions: of oxidation may; vary depending upon? the particular: extnactioir-systenii to:- he used: Advantageous results:' may: be obtained: by passing air t-hroug-h: the; tall 0nwhil'era maintaining: an elevated: temperature of about 60 tor abtiut 150 Particularly; advantageousrre-s sults may: be: obtained. at" temperatures; of! between. about C. to.-ab'out Thea-most:advantageousmanner ofidetenminingvthe. degree of oxidation. to he desired: is by measuring: the viscosity of-the material: subjected: to oxidizing, conditions.- xidiz'edis: comprised essentially ofthe unsaturated com?- ponents: of the. ori'ginalltalh oil; namely, those which: con:- tain carbon to: carbon" double: bonds. 'The: principal constituents of? the oxidized f-ractioir; are; those: components-of. theiori'ginah tallfoil'which contain two on-r'nore such: double bonds: per molecule:

Inaccordance with one embodimentv of the invention disclosed:- and' claimed in the? above-mentioned. copending application; the; oxidized tall-- oil is; mixed: with a: no polar; solvent-.1 While any; of the: well-known: nonpolar hydrocarbon: solvents: such as. the higher, boiling: aliphatic hydrocarbons; for. examPle-mmixedoctane fraction; aromatic hydrocarbons, for: example benzene, toluene, xylene;v and commercial mixtures of straight chain. and aromatic. hydrocarbons may be used, the desired-results have. been obtained by means ofa petroleum naphtha. Generally. speaking, higher, boiling solvents; such as those boiling betweenabout E. to-about 3.00. F. are preferred-as these may beeasily removedfromtheir extracts.

In another embodiment of, the invention disclosed in said copendingapplication, the, oxidized tall oil. is dissolved, in a polar solvent and, thereafter extracted with a. nonpolar solvent. In thisembodiment of. that inven: tion, a. wide variety of polar solvents may beemployed. The polar solvents may contain. a hyd dili glroup such as. methyl, alcohol, ethylene glycol, propylene. glycoL, and glycerine. They may contain liyd'roxy esters. such as beta-hydroxy ethyl acetate. They may contain a carboxyl group such as formic acid and acetic acid; They may containan' aldehyde group such as benzaldehyde. They may contain a carbonyl group such as acetone. They may be ethers, for example dimethoxy tetraglycol.

When the oxidized tall-z-oil: is= first dissolved in a polar solvent and then extracted with nonpolar solvent, the

I polar solvent fraction is then freed of solvent and the The. fraction of tall: oi'II Which is resulting material is substantially completely free of saturated fatty acids.

In still a third embodiment of the invention disclosed in said copending application, the fractionation of the oxidized tall oil may be carried out by partition chromatographic separation' In accordance with this particular embodiment of that invention. a suitable column is provided and charged with an adsorbent material such as finely divided dehydrated silica which has been impregnated with an equal weight of polar solvent and then mixed into a slurry with'nonpolar solvent which had been previously saturated with polar solvent. This slurry is charged to the column, and the ads rbent and n npolar solvent separate to obtain the desired partition column. When the nonpolar solvent has settled to the level of the adsorbent, a mixture of oxidized tall oil and nonpolar solvent is added. When the tall oil has passed down to the level of. the adsorbent, more nonpolar solvent is added to developthe column. Generally speaking, three bands develop within the column. The first band passes through the column rapidly and is collected at the discharge end. The column may then be broken up to separate the two remaining bands and each is eluted from the adsorbent by means of a suitable solvent such as acetone or other low boiling oxygen-containing solvents. The resulting fractions include a partially oxidized unsaturated fatty acid and resin acid fraction which is substantially completely free of saturated fatty acids and sterols.

In the practice of my invention tall oil fractions which are substantially completely free from saturated fatty acids and which are advantageously obtained in accordancewith the above-mentioned application may be admixed with rosin or other resins generally utilized in the manfacture of linoleum cement, for example, copal, kauri gum, congo gum, other naturally occurring resins, and synthetic resins, such as urea formaldehyde resins, phenol formaldehyde resins, resinous petroleum derivatives, such as still residues from refining of petroleum fractions and the like, and any drying or semi-drying oil commonly employed in the manufacture of such cements, and the resulting mixture may be oxidized in conventional cement-making equipment to'produce a highly desirable binder which can be compounded with other ingredients to produce linoleum compositions in the conventional manner. I have obtained particularly advantageous results by subjecting to oxidation conditions a mixture containing about to 30% by weight of an extract as defined hereinabove, about 13% to 21% by weight of a natural resin such as rosin, and about 57% to 69% by weight of a drying or semi-drying oil. When less than 10% by weight of the oxidized tall oil fraction is employed, no significant improvement can be noted over the compositions containing crude tall oil. When more than 30% by weight of the oxidized fraction is utilized, linoleum made from compositions containing the cement tends to be tacky and is less resistant to soiling. In addi tion, heavy gauge linoleums lack resistance to indentation particularly at elevated temperatures.

Generally speaking, conventional conditions of cement preparation are followed in preparing the cements "of my invention. For instance, the mixture is charged to a mechanical oxidizer and blown with air while being agitated at a temperature between about 160 F. and 240 F. The material is subjected to these conditions for a period of about 24 hours or more.

In order to more fully understand my invention reference may be had to the'following specific examples which are given by way of illustration and not by way of. limi tion. r

Example I A linoleum cement was prepared by mechanically oxidizing for about 21 hours a mixture contaimng the fol lowing ingredients in the following proportions, by weight:

Parts by weight Saturated fatty acid free fraction of oxidized tall 011 50 Rosin 10S Linseed oil 345 Manganese and lead driers 1.016

Example 11 A desirable linoleum .cement was prepared by mechanically oxidizing for about 26 hours a mixture containing the following ingredients in the following proportions:

Parts by weight Saturated fatty acid free fraction of oxidized tall oil Rosin 65 Linseed oil 285 Manganese and lead driers 1.016

Wood flour- 73 Whiting 1 17 Cement l 12 Such linoleum compositions have been calendered into sheets and the sheets were cured and evaluated with respect to their property of indentation resistance at 77 F. and 115 F. The average percent change in the percent indentation of samples made in accordance with my invention was 44.2%. The average percent change in the percent indentation of samples made from crude tall oil was 49.2%. The average percent change in the percent of indentation of a typical linoleum cement made from linseed oil and rosin was about 45%. These figures indicate that linoleum cements made in accordance with my invention are equal to or better than conventional cements and are significantly superior to linoleum cements made from crude tall oil. In addition to the improvement in resistance to indentation the material is characterized by good resiliency and flexibility, which property is highly important as a hard surface floor covering.

As used herein,'the term siccative oil or its equivalent is intended to include drying oils and semi-drying oils.

While I have described my invention with reference to certain particular embodiments and with reference to certain specific examples, it is 'to be understood that the invention is not limited thereby. Therefore, changes, omissions, substitutions and/ or additions may be made without departing from the spirit of the invention as defined in the appended claims which are intended to be limited only as required bythe prior art.

v r I claim: I

1. A composition of matter suitable for use in the manufacture of linoleum cements by oxidation at a temperature'of about F. to about 240 F. and comprising about 10% to. 30% by weight of an oxidized fraction of tall oil which is comprised essentially of the oxidized unsaturatedcomponents of tall oil and which is substan tially completely free from saturated fatty acids and which has a viscositybetween about 15 seconds and 250 seconds, about 13% to 21% by weight of rosin, and about 57% to 69% by weight of a siccative fatty oil.

2. A linoleum cement comprised essentially of the product obtained by-mechanically oxidizing at a temperature of about 160 F. to about 240 F. a mixture containing about 10% to 30% by weight of an oxidized tall oil fraction which is comprised essentially of the oxidized unsaturated components of tall oil and which is substan- 5 tially completely free from saturated fatty acids and which has a viscosity between about 15 seconds and 250 seconds, about 13% to 21% by weight of rosin, and about 57% to 69% by weight of linseed oil.

3. A linoleum composition comprising a filler and a binder obtained by mechanically oxidizing at a temperature of about 160 F. to about 240 F. a mixture including about 10% to 30% by weight of an oxidized fraction of tall oil which is comprised essentially of the oxidized unsaturated components of tall oil and which is substantially completely free from saturated fatty acids and which has a viscosity between about 15 seconds and 250 seconds, about 13% to 21% by weight of rosin, and about 57% to 69% by weight of a siccative fatty oil.

References Cited in the file of this patent UNITED STATES PATENTS 2,111,259 Blengsli Mar. 15, 1938 2,439,377 Bare et a1. Apr. 13, 1948 2,565,484 Dunlap et a1 Aug. 28, 1951 2,594,345 Powers et a1 Apr. 29, 1952 OTHER REFERENCES 

1. A COMPOSITION OF MATTER SUITABLE FOR USE IN THE MANUFACTURE OF LINOLEUM CEMENTS BY OXIDATION AT A TEMPERATURE OF ABOUT 160F. TO ABOUT 240*F. AND COMPRISING ABOUT 10% TO 30% BY WEIGHT OF A OXIDIZED FRACTION OF TALL OIL WHICH IS COMPRISED ESSENTIALLY OF THE OXIDIZED UNSATURATED COMPONENTS OF TALL OIL AND WHICH IS SUBSTANTIALLY COMPLETELY FREE FROM SATURATED FATTY ACIDS AND WHICH HAS A VISCOSITY BETWEEN ABOUT 15 SECONDS AND 250 SECONDS, ABOUT 13% TO 21% BY WEIGHT OF ROSIN, AND ABOUT 57% TO 69% BY WEIGHT OF SICCATIVE FATTY OIL. 